2, 2-dichloro-3(2h)-furanones and the preparation of aryl-pyruvic acid therefrom



United States Patent This application-is a continuation-in-part of copending application Serial No. 229,990,1iled October-11, 1962, now abandoned.

This invention relates to newand useful 2,2-dichloro- 3(2H)'-furanones of the formula o1ro wherein n is a number from 0 to 1,,wherein R is an aromatic radical and wherein --N is, a secondary amine residue. These materials are pro-emergent herbicides? for broad leaf and/or narrow leaf plants. Additionally those of the foregoing formula wherein n is Oare useful in preparing substituted pyruvic acids of the formula wherein R has the aforedescribed significance'by the mineral acid hydrolysis thereof.

The said ,2,2-dichlor0-3(2H)furanones areprepared from oxalyl chloride and an assubstituted acetamide of the formula wherein R and n have the aforedescribedsignificance and wherein --N is a secondary amine residue, e.g. a

(1) Saturated single ring heterocyclic amine residue of the formula ta N'- yJ wherein A is CH CH OCH CH CH CH SCH CH or alkylene of from 4 to carbon atoms-and having from 4 to 6 carbon atoms in a continuous chain between the valence bonds, or a (2) Secondary amine residue of the formula G wherein M and G are like or unlike hydrocarbyl radicals having 1 to 10 carbon atoms such as the various aryl, alkaryl, aralkyl or alkyl radicals or said hydrocarbyl radicals having at least one substituent such as lower alkoxy, chlorine or bromine. As illustrative of such radicals are methyl, ethyl, propyl, butyl, amyl, octyl, decyl, benzyl, phenethyl, phenbutyl, phenyl, naphthyl, tolyl, xylyl, ethylphenyl, propylto-lyl, butylphenyl, and the various isomeric forms thereof, methoxyethyl, eth- -oxyethyl, propoxyethyl, methoxyphenyl, ethoxyphenyl,

diethoxyphenyl, chloroethyl, chlorobutyl, dichloropropyl,

"ice

trichlorobutyl, ar-chlorobenzyl, ar-dichlorobenzyl, ardichlorophenethyl, chlorophenyl, ar-chlorotolyl, chloronaphthyl, dichlorophenyl, trichlorophenyl, bromoethyl, bromoamyl, bromophenyl, dibromophenyl, tribromophenyl, bromodichlorophenyl, ar-chloroanisyl, ar-chlorophenetyl, and the various isomeric forms thereof.

The aforesaid 2,2-dich1oro-3(2H)-furanones are prepared by reacting oxalyl chloride with an a-substituted acetamide of the aforedescribed formula wherein R is an aromatic hydrocarbyl (a) radical having 6 to 12 carbon atoms, e.g. phenyl, tolyl, xylyl, ethylphenyl, propylphenyl, propyltolyl, butylphenyl, hexylphenyl, biphenylyl, naphthyl, methylnaphthyl and said aromatic hydrocarbyl (a) having at least one chlorine or bromine substituent or mixtures thereof on the aromatic carbocyclic nucleus thereof. As illustrative of operable a-substituted acetamide reactants are N-(phenoxyacetyl) morpholine, N-(naphthoxyacetyl) morpholine, N-(m-tolyloxyacetyl) morpholine, N-(phenoxyacetyl) pyrrolidine, N-(phenoxyacetyl) piperidine, N-(3,5-Xylyloxyacetyl) piperidine, N-(phenoxyacetyl) alphapipecoline, N-(phenoxyacetyl) betapipecoline, N-(phenoxyacetyl) gammapipecoline, N-(phenoxyacetyl) alpha, gammalutidine, N-(phenoxyacetyl) 2,4-dimethylpyrrolidine, N-(phenoxyacetyl) 3-ethyl-4-methylpiperidine, N-(phenoxyacetyl) 4-isobutylpiperidine, N-(phenoxyacetyl) 3-butyl-2-methylpiperidine, N-(phenoxyacetyl) hexamethyleneimine, N-(4-chlorophenoxyacetyl) hexamethyleneimine, N,N-dimethyl alphaphenoxyacetamide,

N,N-dimethyl alpha(4-biphenyloxy)acetamide,

N',N-dimethyl alpha-(4-chlorophenyloxy) acetamide, N,N-diethyl alphaphenoxyacetamide,

N-ethyl-N-methyl alphanaphthoxyacetamide,

N,N-di-n-butyl alphaphenoxyacetamide,

N,N-diisoamyl alpha-(2,4-dichlorophenoxy) acetamide,

N,N-di-n-decyl .alphaphenoxyacetamide, N-methyl-N-phenyl alphaphenoxyacetamide, N-methyl-N-benzyl alphaphenoxyacetamide,

N-ethyl-N-p-tolyl alphaphenoxyacetamide,

N,N-dibenzyl alphaphenoxyacetamide, N,N-di-betaphenethyl alpha-(3,5-xylyloxy) acetamide, N,N-diphenyl alphaphenoxyacetamide,

N,N-dinaphthy1 alphaphenoxyacetamide,

N-ethyl-N-naphthyl alphaphenoxyacetamide,

N,N-di(ethoxyethyl) alphaphenoxyacetamide,

N,N-di(2-ch1oroethyl) alphaphenoxyacetamide, N,N-di(4-chlorophenyl) alphaphenoxyacetarnide,

N*,N di(2,4-dichloropheny1) alphaphenoxyacetamide,

N-(phenacetyl) 4-isobutylpiperidine, N-(phenacetyl) 3-butyl-2-methylpiperidine, N-(phenacetyl) hexamethyleneimine, N-(4-chlorophenacetyl) hexamethyleneimine, N,N-dimethyl alphaphenacetamide, N,N-dimethyl alpha-(4biphenyl)acetarnide, N,N-dimethyl alpha-(4-chlorophenyl)acetaimide, N,N-diethyl alphaphenacetamide, N-ethyLN-methyl alphanaphthacetarmide, N,N-di-n-butyl alphaphenacetamide, N,N-diisoamyl alpha-(2,4-dichlorophen) acetamide, N,N-di-n-decyl alphaphenacetamide, Nmethyl-N-phenyl alphaphenacetamide, N-methyl-N-benz'yl alphaphenacetamide, N-ethyl-N-p-tolyl alphaphenacetarnide, N,N-dibenzyl alphaphenacetamide, N,N-di-betaphenethyl alpha-(3,5-xylyl) acetamide, N,N-diphenyl alphaphenacetamide, N,N-din'aphthyl alphaphenacetamide, 'N-ethyl-N-naphthyl alphaphenacetamide, N,N-di(ethoxyethyl) alphaphenacetamide; N,N-di(2-chloroethyl) alphaphenacetamide, N,N-di(4-chlorophenyl) alphaphenacetamide, N,N-di(2,4-dichlorophenyl) alphaphenacetamide, N-methyl-N-4 chlorophenyl alpha-(4-biphenyl) acetamide', N-methyl-N-(3 bromo-4-anisyl) alphaphenacetamide, N-ethoxyethyl-N-(2-chloro-4-bromophenyl) alphaphenacetamide, etc.

While the oxalyl chloride acid and the tat-substituted acetamide reactant theoretically react in a molar ratio of 2:1 an excess of either reactant can be employed where and when desired, e.g. 1.5 to 2.5 moles of oxalyl chloride per mole of u-substituted acetamide. range of reaction temperatures can be employed provided the reaction system is fluid :(i.e. maintained at a temperature above the freezing point of the system up to and including the systems boiling point) reaction'tem- While a wide peratures in the range of 0 C. to 100 C. are preferred. i

of water present to conduct the hydrolysis will be at least three moles per mole of the 2,2-dich1oro-3(2H)- furanone, however to increase the rate of hydrolysis amounts up to 25 moles of water per mole of 2,2-dichloro-3(2H)-furanone can be employed. .The amount of mineral acid in the anhydrous form can vary widely but usually will be in the weight range of 5 parts to 20-parts per 100 parts of water. While a wide range of reaction temperatures can be employed provided the reactionsystem is fluid (i.e. maintained at .a temperature above 4 As illustrative of the. instant invention is the following:

' EXAMPLEII To a suitable reaction vessel equipped with an agitator, thermometer'and reflux condenser is charged 19.1 parts by weight (substantially 0.1 mole) of N,N-diethylalphaphenacetamide and approximately 140 parts by weight of methylene chloride.- While maintaining'the so-charged mass at about 0 C. and with. agitation 25.4 parts by Weight- (substantially 0.2 rnole) of oxalyl chloride is added dropwise.= Upon completion of the'oxalyl .chlo-- ride addition thereaction mass is agitated at room tern The reaction mass is :then evaporated under reduced pressure.

is dissolved in.acetone andtreated with charcoal? The. mass is cooled to 5 C. .andthe addition of water separated a tan solid. Recrystallization of this solid from. Y acetone-wateryielded- 17.2 parts by weight of S-diethyl-v perature for about three hours.

The solid residue amino-2,2-dichloro-4-phenyl-3(2H)-furanone,. M.P. 1119+ 121 C. AnalysisP-Theoretical 4.67 N, 23.62% 01;?

Found 4.76 N, 23.65 %.Cl.

EXAMPLE IA:

To a suitable reaction vesselequipped with an agita-. tor is charged .80 parts by weight: of :5-diethylamino- 2,2-dichloro 4-phenylr3(2H:) furanone, approximately parts byweight of acetone. and approximately parts by weight of 10% by weight hydrochloric acid.i

The so-charg ed mass is heated to fthe reflux temperature and refluxed for 24 hours. The resultant mass is extracted with diethyl ether, and the extract washed with saturated aqueous sodium bicarbonate until carbon dioxide-ceased'evolving, The wash is then acidified with 12N HCl and then-extractedwith diethyl ether. The

ether extract is dried over anhydrous magnesium sulfate-.:

EXAMPLELII Employing theiprocedu're of Example I but replacing N,N-diethyl alphaphenacetamide with an equirnolecular amount of 'N (l naphthylacetyl) hexamethyleneimine there is obtained 5-hexamethyleneimino+2,2+dichloro-4-- (l-naphthyl)-3-(2H)-furanone. This material on bydrolyzing in accordance with the procedure of Example yields 1-naphthyl)-pyruvic acid.

EXAMPLE -III Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equirnolecular amount of N-ethyl-N-(4 chlorophenyl) alphaphenaceta- 'mide there is obtained 5 (N-ethyl-N 4-chlorophenylamino)-2,2-dichloro-4-phenyl-3 (2H) -furanone. This qua-- terial on hydrolyzing'in accordance with the procedure of Example IA yields phenylpyr uvic acid.

EXAMPLE fIV Employing the procedure of Example I but replacing N,N-diethyl 'alphaphenac'etamide with an equimolecular amount of N,N di(2-ethoxyethyl) alpha-p-tolylacetamide there is obtained 5-di(2-fe'thoxyethyl)amino-2,2-dichloro- 4-(4-tolyl-)-3(2H)-furanone.: This material on hydrolyzing .in accordance with the procedure'of Example yields (4-tolyl;):-pyruvic acid.

EXAMPLE V Employing the, procedureof Example I'but' replacing N,N-diethyl alphaphenacetamide with an equirnolecular amount of N'-methyl-N-ethyl alpha-,(ZA-dichlorophen) acetamide there is obtained :5-(Nmethyl-N-ethylamino)- 2,2-dichloro-4-(2,4 dichlorophenyl 3(2H) furanone.

This material on .hydro1yzing in accordance. with the procedure of Example IA yields (2,4-dichlorophenyl)-pyruvic acid.

EXAMPLE VI Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N-(phenacetyl) morpholine there is obtained 5- (4-rnorpholino -2,2-dichloro-4-phenyl-3 (2H) -furanone.

EXAMPLE VII Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N-isopropyl-N-(3-chlorophenyl) alphaphenacetamide. there is obtained S-(N-isopropyl-N-3-chlorophenylamino -2,2-dichloro-4-phenyl-3 (2H -furanone.

EXAMPLE VIII Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N,N-dibenzyl alphaphenacetamide there is obtained 5- (N,N-dibenzylamino)-2,2-dichloro 4 phenyl- 3 2H -furanone.

' EXAMPLE X Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N-methyl-N-phenyl alphaphenacetamide there is obtained 5-(N-methyl-N-phenylarnino)-2,2-dichloro-4- phenyl-3 (2H) -furanone.

EXAMPLE XI EXAMPLE XII Employing the procedure of Example I but replacing N,N-diethylalphaphenacetamide with an equimolecular amount of N-methyl-N-phenyl alpha-(2,4-dichlorophenyl) acetamide there is obtained S-(N-rnethyl-N-phenylamino)-2,2-dichloro 4 (2,4 dichlorophenyl) 3.(2H)- furanone.

EXAMPLE XIII Employing the procedure-of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N-methyl-N-phenyl alpha-(4-methylphenyl) acetamide there is obtained 5-(N-methyl-N-phenylamino)- -'2,2-dichloro-4-(4-methylphenyl)-3(2H) furanone (M.P.

EXAMPLE XIV Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N,N-diethyl alpha-(3,4-dichlorophenyl) acetamidethere is obtained 5-diethylamino-2,2-dichloro- 4-(3,4-dichlorophenyl)-3('2H)-furanone. This material on hydrolyzing in accordance with the procedure of Example IA yields (3,4-dichlorophenyl) pyruvic acid.

EXAMPLE XV Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N-methyl-N-phenyl alphaphenoxyacetamide there is obtained 5-(N-methyl-N-phenylamino)-2,2- dichloro-4-phenoxy-3(2H)-furanone (M.P. 109-1l1 C.).

EXAMPLE XVI Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N,N-diethyl alphaphenoxyacetamide there is obtain-ed 5(N,N diethylamino)-2,2 di-chloro-4-phenoxy- 3(2H)-furanone (M.P. 95.5-96.5 C.).

EXAMPLE XVII Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecw lar amount of N-methyl-N-p'henyl ralpha-(2,'4-dich-lorophenoxy)acetamidethere is obtained 5 (N methyl-N- :phenylamino) 2,2 dicl'rlono 4 (2,4-diohlorophen=oxy)-3- (2H)-furanone (M.P. l52154 C.).

EXAMPLE XVIII Employing therprocedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N-(phenoxyacetyl) morpholine there is obtained 5 4-morpholino) -2,2-dichloro-4-phenoxy-3 (2H furanone.

EXAMPLE XIX Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecw lar amount of N-isopropyl.-N-(3-chlorophenyl) alphaphenoxyacetamide there is obtained 5-(N-isopropyl-N-3- chlorophenylamino) 2,2-dichlolro-4-phenoxy-3 (2H -fi1ranone.

EXAMPLE XX Employing the procedure of Example I but replacing N,N-diethyl alphaphenacetamide with an equimolecular amount of N,N-diphenyl alphaphenoxyacetamide there is obtained 5-diphenylamino-2,2-dichloro-4-phenoxy-3 (2H) furanone.

As aforementioned the 2,2-dichloro-3 (2H)-furanones are effective pre-emergent herbicides. For example at an application rate to soil of 25 pounds per acre, respectively, (I) the product of Example I exhibited complete control of narrow leaf plants such as crab grass and foxtail, (2) the product of Example XV exhibited complete control of crab grass, 'foxtail and pigweed, (3) the product of Example VIII exhibited complete control of sugar beet, pigweed, radish and morning glory, (4) the product of Example XVI exhibited complete control of sugar beet and pigweed, and (5) the product of Example XVII which was particularly outstanding in the complete control of sugar beet, foxtail, crab grass, pigweed, soybean and tomato.

Of the 2,2-dichloro-3 (2H)-furanones of this invention those of the formulae o=o-( 0 n o1,o C-NM (CH mu and O=CC(O) 11""(0111010 substitued phenyl) where m and n, respectively, are numbers from 0 to 1, wherein M and G, respectively, are alkyl having from 1 to 10 carbon atoms, and wherein chloro substituted phenyl has from 1 to 3 chlorine substitutes are particularly useful in the pre-emergent control of noxious vegetation.

While this invention has been described with respect to certain embodiments it is to be understood that it is not so limited and that variations and modifications thereof obvious to those skilled in the art can be made without departing from the spirit or scope of this invention.

' furanone. H I

7 What is claimed is: 1. A compound of the formula =o--o-(o ,.R

m. AN-

wherein A is selected from the group consisting of' -CH CH OCH CH CH CH SCH CH and alkylene of the 4 to 10 carbon atoms and having from 4 to 6 carbon atoms in a continuous chain between the valence bonds, and a (2) Secondary amine residue of the formula wherein M and G are selected from the group consisting of (3) Hydrocarbylhaving from 1 to 10 carbon atoms selected from the group consisting of alkyl, phenyl substituted alkyl, phenyl, alkyl substituted phenyl, and naphthyl, and v (4) Said hydrocarbyl (3) being substituted with. a

member of the class consisting of lower alkoxy, chlorine and bromine.

2. A compound of the formula wherein m is a number from 0 to 1 and wherein Mand G respectively are alkyl having from 1 to 10 carbon atoms. a

3. A compound of the formula O=O CH (chlor0 substitutedphenyl) ono O-N-phnyl 0 Ha wherein chloro substituted phenyl has from 1 to 3 chlorine substituents.

4. A compound of the formula wherein m is a number from 0 to 1 and wherein Mand G respectively are alkyl having from 1 to 10 carbon atoms. a

5. A compoundof the formula O=C--OO(chloro substituted phenyl) wherein chloro substituted phenyl has from 1 to 3 chlorine substituents. I

6; diethylamino 2,2

dichloro 4 phenyl 3 (2H)- amine residue 7. 5 (N-methyl N phenylamino)-2,2-dichloro-4-(4-- methylphenyl -3 (2H -furanone.

8H5 (N-methyl-N-phenylamino)-2,2-dichloro-4-(2-,4-

dichlorophenoxy) -3 2H -furanone.'

9.55 diethylamino 2,2 dichloro-4 -phenoxy-3 (2H)- furanone.

10. 5 (N methyl N phenylamino)-2,2-dichloro-4- phenoxy-3 (2H)-furanone.

11.: The method .of'making a compound of the formula 0=CC(0),,R

wherein n is a number from O-to 1, wherein R is hydrocarbyl having 6 to 12 carbon atoms and selected fromr th group consisting of (a) phenyl, alkyl substituted ph'enyl; biphenylyl, naphthyl, and methylnaphthyhand (b) saidv hydrocarbyl (a) being substituted ion the aromatic carbocyclic nucleus thereof with 'substituents of the .class consisting ofchlorine and bromine, and wherein 'N is a secondary amineresidue selected from the group consisting of a (1) Saturated single ring heterocyclic amineresidue of the formula.

m g A J wherein A is, selected from the group consisting of ;CH CH OCH CH CH CH S CH CH T-, and al kylene of from 4 to 10 carbon atoms and .havingtfrom 4 to 6 carbon atoms .in a continuous. chain between the valence bonds,,and a (2) Secondary amine residue of the formula wherein M andG are selected from. the group consisting (4) Said hydrocarbyl (3) being substituted with ja member of the class consisting oflower alkoxy; chlorine and bromine, which comprises reacting oXalyl chloride with an a-substituted acetamide of-the formula;

R- o OH 'C'-N 2 up wherein R,-,n and 'N have the'same significance as above.

12. The method of vclaim ll attended by the step of hydrolyzing the 2,2-dichloro-3(2H)-furanone product thereof wherein n is 0 in the presence of a mineral acid.

wherein R has the same significance as in claim 11.

13.= The method of making phenyl-pyruvic acid which comprises hydrolyzing a 2,2,4-trichloro-3(2H).;furanone of the formula wherein M and Grespectively are alkylhaving 1 to. 10 carbon atoms in thepresence of a mineralacid.

14. :The method of making a compound of the formula O=C-C( O) n-(chloro substituted phenyl) C]3C C-I;lphenyl i O (3 Hydrocarbyl having 1 to :10 carbon atoms selected from the group consisting of alkyl, plienyl substituted. alkyl, phenyl, alkyl substituted phenyl, and naphthyl, and

9 wherein n is a number from 0 to 1 and wherein chloro substituted phenyl has from 1 to 3 chlorine substituents which comprises reacting oxalyl chloride with an a-substituted acetamide of the formula (chloro substituted phenyD-(O) n (|3|Nphenyl wherein n and chloro substituted phenyl have the aforedescribed significance.

wherein m and n, respectively, are numbers from O to 1 and wherein M and G, respectively, are alkyl having from 1 to 10 carbon atoms which comprises reacting oxalyl chloride with an DL-SubStitUted acetarnide of the formula wherein m, n, M and G have the aforedescribed significance.

No references cited.

NICHOLAS S. RIZZO, Primary Examiner. 

1. A COMPOUND OF THE FORMULA
 11. THE METHOD OF MAKING A COMPOUND OF THE FORMULA WHEREIN N IS A NUMBER FROM 0 TO 1, WHEREIN R IS HYDROCARBYL HAVING 6 TO 12 CARBON ATOMS AND SELECTED FROM THE GROUP CONSISTING OF (A) PHENYL, ALKYL SUBSTITUTED PHENYL, BIPHENYLYL, NAPHTHYL, AND METHYLNAPHTHYL, AND (B) SAID HYDROCARBYL (A) BEING SUBSTITUTED ON THE AROMATIC CARBOCYCLIC NUCLEUS THEREOF WITH SUBSTITUENTS OF THE CLASS CONSISTING OF CHLORINE AND BROMINE, AND WHEREIN -N< IS A SECONDARY AMINE RESIDUE SELECTED FROM THE GROUP CONSISTING OF A (1) SATURATED SINGLE RING HETEROCYCLIC AMINE RESIDUE OF THE FORMULA
 12. THE METHOD OF CHAIN 11 ATTENDED BY THE STEP OF HYDROLYZING THE 2,2-DICHLORO-3(2H)-FURANONE PRODUCT THEREOF WHEREIN N IS 0 IN THE PRESENCE OF A MINERAL ACID TO AN ARYL-PYRUVIC ACID OF THE FORMULA 